Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study

Abstract

Uranium | Thorium | Tripodal ligand |Computational chemistry | Electronic structureThe issue of covalence of actinide complexes remains controversial to date. The introduction of 2-phosphaethynolate anion into actinide complexes is expected to investigate the reaction mode and the bonding property. Herein, we describe the functionalization of An(Tren TIPS )Cl (1: An = U; 2: An = Th) precursors with NaOCP(dioxane) 2.5 through salt-elimination method leading to the formation of the corresponding uranium and thorium phosphaethynolate species: [U(Tren TIPS )(OCP)] ( 3) and [Th(Tren TIPS )(OCP)] (4). These two complexes were fully characterized by nuclear magnetic resonance (NMR), FT-IR spectrum, UV-vis-NIR spectroscopies as well as X-ray crystal diffraction. Computational analyses of the two complexes reveal that the U-O bond has a more covalent bond property than the Th-O bond due to more 5f orbital contribution for U.

Theoretical insights into the separation of Am(iii)/Eu(iii): designing ligands based on a preorganization strategy

“…The actinide computational chemistry can provide reliable results for the more complicated actinide complexes using the state-of-the-art computational methods thanks to its rapid development. 29–34 We optimized the structures of the four ligands, the coordination structures and the bonding nature between Am( iii )/Eu( iii ) and ligands as well as explored their Am( iii )/Eu( iii ) separation performance at the level of theory. This work provides useful information on the selectivity for An( iii )/Ln( iii ) separation of the N-heterocyclic ligands based on the preorganization strategy.…”

Synthesis and reactivity of a uranium(iv) complex supported by a monoanionic nitrogen–phosphorus ligand

“…Consequently, a series of new ligands with N and O coordination sites were designed and used in the development of actinide organometallic chemistry. [5][6][7][8][9][10][11][12][13][14][15][16][17][18] For instance, since the first example of an actinide complex supported by a triamidoamine ([(RNCH 2 CH 2 ) 3 N] 3− ) ligand (Tren) was reported by Scott and co-workers in 1994, 19 actinide organometallic chemistry with Tren ligands has flourished. 18,[20][21][22][23][24][25][26] With these trianionic ligands, a series of trivalent uranium complexes were isolated.…”

“…[5][6][7][8][9][10][11][12][13][14][15][16][17][18] For instance, since the first example of an actinide complex supported by a triamidoamine ([(RNCH 2 CH 2 ) 3 N] 3− ) ligand (Tren) was reported by Scott and co-workers in 1994, 19 actinide organometallic chemistry with Tren ligands has flourished. 18,[20][21][22][23][24][25][26] With these trianionic ligands, a series of trivalent uranium complexes were isolated. 24,25,27,28 In 2019, we found that a novel phosphine-substituted Tren ligand (L1, Fig.…”

A Theoretical Study of Unsupported Uranium–Ruthenium Bonds Based on Tripodal Ligands

“…The tripodal ligand as a pocket scaffold plays a key role in immobilizing the metal ion because of its multidentate coordination, such as the typical triamidoamine (Tren) ligand. − The uranium complexes with an ancillary tripodal ligand are the most versatile in uranium–ligand multiple bonds, uranium–metal bonds, small molecule activation, etc . Metal–metal (M–M) bonds represent an important branch of Werner’s classical coordination theory, , which is also an interesting organometallic chemistry research field.…”